KR20090104671A - Color filter, method of producing the same, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A color filter, a manufacturing method thereof, and a liquid crystal display device are provided to obtain an image with high quality by improving a voltage maintaining rate of the color filter. CONSTITUTION: A color filter has a color pixel and a black matrix. The color pixel has two colors patterned on a substrate. A color liquid compound is formed on the substrate to form one color pixel or black matrix. The remaining solvent of the color liquid compound layer after the pre-baking is 10 ul/m^2 or less. The total of the remaining solvent quantity of each color pixel and the color liquid compound layer is below 40 ul/m^2 or less. The color liquid composition layer forms the black matrix.

Description

COLOR FILTER, METHOD OF PRODUCING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention provides, for example, a color filter having a black matrix (K) in which dot-like pixels such as red (R), green (G), and blue (B) are arranged in a matrix on a substrate such as glass, and a manufacturing method thereof; And a liquid crystal display device.

The color filter is an essential component of a liquid crystal display or a solid state image pickup device.

For example, a liquid crystal display (LCD) color filter requires a liquid crystal display to be used for a TV, so that a higher quality image quality is required than that of a conventional notebook or display application.

As a method of manufacturing a color filter in connection with the above-mentioned image quality improvement, conventionally (1) dyeing method (2) printing method (3) coating, exposure, and development of colored photosensitive resin liquid, and a method of forming a pattern image colored by developing ( Coloring resist method; for example, see Japanese Patent Application Laid-Open No. 63-298304, Japanese Patent Application Laid-Open No. 63-309916, and Japanese Patent Application Laid-Open No. Hei 1-52449), and (4) apply a colored photosensitive resin liquid onto a support in advance. A photosensitive colored layer is formed, and the photosensitive resin is directly transferred onto a final or cutting material, exposed, and developed to form a colored pattern (transfer method). 61-99102). Moreover, the method of using the inkjet method is also known (for example, refer Unexamined-Japanese-Patent No. 8-227012).

Moreover, the technique which uses the photosensitive composition containing the pigment whose voltage retention is 80% or more as a coating composition for RGB pixel formation in order to solve the display defect at the time of image display is disclosed (for example, Unexamined-Japanese-Patent No. 2000-329929). Reference). Moreover, the transfer film technique whose amount of residual solvent in the layer formed from the photosensitive composition is 0.001%-0.2% is disclosed.

However, in the method described in Japanese Patent Laid-Open No. 2000-329929, display defects are improved by using a pigment selected or treated so that the voltage holding ratio is 80% or more, and in the method described in Japanese Patent Laid-Open No. 2005-181858 Although transferability is improved by using the transfer film whose amount of residual solvent in the layer formed by 0.001%-0.2% is used, it is not disclosed that the residual solvent of the photosensitive composition affects voltage retention in all. In addition, it is not disclosed that the residual solvent of the photosensitive composition affects developability.

In view of the above circumstances, the present invention improves the developability by reducing the amount of residual solvent in the colored liquid composition layer immediately after prebaking, and also improves the voltage retention of the color filter obtained, thereby producing a color filter capable of obtaining a high quality image. An object thereof is to provide a method, a color filter obtained thereby, and a liquid crystal display device using the color filter.

The specific means for achieving the said subject is as follows.

<1>

A method of manufacturing a color filter having two or more patterned colored pixels having different colors on a substrate and a black matrix around the substrate, wherein the colored liquid composition is formed on the substrate to form the one or more colored pixels or black matrix. The residual solvent amount of the colored liquid composition layer immediately after formation and prebaking is 10 µl / m 2 or less, and the total sum of the residual solvent amounts of the colored liquid composition layer for forming the colored pixels and the black matrix of each color is 40 µl / The manufacturing method of the color filter characterized by the above-mentioned.

<2> The method for producing a color filter according to <1>, wherein the method for forming the colored liquid composition is any one of a spinner method and a slit coater method.

<3> The method for producing a color filter according to <1>, wherein the prebaking temperature is 60 ° C. or more and 140 ° C. or less, and the prebaking time is 30 seconds or more and 300 seconds or less.

<4> The color filter obtained by the manufacturing method as described in <1>.

<5> The color filter obtained by the manufacturing method as described in <1>, The solvent of the said colored liquid composition contains 30-70 weight% of solvents with a boiling point of 100 degreeC or more.

<6> The color filter obtained by the production method according to <1>, wherein the solvent of the colored liquid composition is selected from propylene glycol monomethyl ether acetate, cyclohexanone, methyl ethyl ketone and 3-ethoxyethyl propionate. Color filter, characterized in that at least one.

<7> The color filter obtained by the manufacturing method as described in <1>, The said colored liquid composition contains the polymer which has a carboxylic acid in a side chain, The color filter characterized by the above-mentioned.

<8> The color filter according to <7>, wherein the colored liquid composition further contains an epoxy resin.

<9> The color filter obtained by the manufacturing method described in <1>, wherein the colored liquid composition contains a colorant having an average particle size of 10 nm or more and 100 nm or less.

<10> Color filter obtained by the manufacturing method as described in <1>, The said colored liquid composition contains the addition polymeric compound which has one or more ethylenically unsaturated double bond.

<11> The color filter obtained by the manufacturing method as described in <1>, The said colored liquid composition contains one or more photoinitiators, The color filter characterized by the above-mentioned.

<12> The color filter obtained by the manufacturing method described in <1>, wherein the colored liquid composition contains at least one polymer dispersant.

<13> The liquid crystal display device characterized by including the color filter obtained by the manufacturing method of <1>.

(Effects of the Invention)

According to the present invention, by reducing the amount of residual solvent in the colored liquid composition layer immediately after prebaking, the developability of the color filter can be improved and the voltage retention of the color filter obtained can be improved to obtain a high quality image. The color filter obtained by this and the liquid crystal display device using the said color filter can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the color filter of this invention, its manufacturing method, and a liquid crystal display device are demonstrated in detail.

<Method of manufacturing color filter>

The method for manufacturing a color filter of the present invention is a method for manufacturing a color filter having two or more patterned colored pixels (hereinafter referred to as colored patterns) having different colors on a substrate and a black matrix around them.

In order to form the at least one colored pixel or black matrix, the residual solvent amount of the colored liquid composition layer immediately after forming and prebaking the colored liquid composition on the substrate is 10 µl / m 2 or less, and the colored pixels and the black matrix of each color. The sum total of the amount of residual solvent of the said colored liquid composition layer for forming is 40 microliters / m <2> or less.

More specifically, for example, the method for producing a color filter of the present invention includes a black matrix forming step and a coloring pattern forming step, and other steps can be provided and configured as necessary. And in this black matrix formation process and a coloring pattern formation process, in order to form a black matrix and a coloring pattern, on a board | substrate, a coloring liquid composition (in the case of a black matrix, it corresponds to the photosensitive deepening composition, and in the case of a coloring pattern, a photosensitive coloring composition. The amount of residual solvent of the photosensitive deepening composition layer (photosensitive deepening composition layer, photosensitive coloring composition layer) immediately after formation is controlled as mentioned above.

In the manufacturing method of the color filter of this invention, the developability is improved by reducing the amount of residual solvent in the colored liquid composition layer immediately after prebaking, and the voltage retention of the color filter obtained can be improved, and a high quality image can be obtained.

Here, the residual solvent amount of the colored liquid composition layer immediately after prebaking is the residual solvent of the colored liquid composition layer (layer before exposure and development) within 5 minutes after applying the colored liquid composition and prebaking and heating and drying. Amount. In addition, the sum total of the amount of residual solvent of a colored liquid composition layer shows the total sum of the amount of residual solvent of each colored liquid composition layer for forming these in the coloring pattern and black matrix of all the colors formed in a color filter.

The residual solvent amount was measured by applying a target colored liquid composition onto a substrate under the same conditions as in the manufacturing process of the color filter, followed by heating to prebaking to prepare a sample of the colored liquid composition layer, which was 10 cm. * 10cm precisely drilled and finely cut. The cut-off thing is put in a vial container, sealed, it is inject | poured into a gas chromatograph, and the amount of residual solvent is computed from the analytical curve previously measured.

In the manufacturing method of the color filter of this invention, it is preferable that the solvent of a colored liquid composition contains 30-70 weight% of solvents with a boiling point of 100 degreeC or more, More preferably, it is 40-60 weight%. In recent years, with the increase in size of LCD panels, for example, a slit coater has been proposed, and the slit coater supplies the colored liquid composition from the slit nozzle to the substrate surface while moving the slit nozzle. If it is included in the above range, the colored liquid composition is dried at the tip of the slit nozzle to prevent the clogging of the nozzle easily, while if it is below the above range, the temperature or time of the prebaking condition of the colored liquid composition layer is reduced. It becomes easy to become low, and price reduction and contact reduction are implement | achieved, and also it is easy to reduce the amount of residual solvent.

Moreover, it is preferable that the solvent of a coloring liquid composition is 1 or more types chosen from propylene glycol monomethyl ether acetate, cyclohexanone, and 3-ethoxyethyl propionate. These solvents are solvents having a boiling point of 100 ° C. or higher, and are suitable in terms of preventing dispersion of the organic pigment in the colored liquid composition and preventing nozzle clogging due to drying of the colored liquid composition at the tip of the slit nozzle in the case of a slit coater. Moreover, although boiling point is 80 degreeC about methyl ethyl ketone, it is suitable at the point of the solubility improvement of the binder polymer in a coloring liquid composition.

Hereinafter, the manufacturing method of the color filter of this invention is divided into a black matrix formation process and a coloring pattern formation process, and it demonstrates in detail.

[Black Matrix Formation Step]

In the present invention, in the black matrix forming step, after the photosensitive deep color composition is applied, prebaking is performed, a photosensitive deep color composition layer is formed on the substrate (photosensitive deep color composition layer forming step), and the photosensitive deep color composition layer is exposed. (Exposure step) After the exposure, the photosensitive deep color composition layer is developed (development step) to form a black matrix pattern, and the formed black matrix pattern is baked (baking step) to form a black matrix. In addition to each of the above steps, the black matrix forming step may be provided with other steps as necessary.

Black matrix

In the present invention, the black matrix preferably has an optical density (OD value) of 2.0 or more and 8.0 or less, more preferably 3.0 or more and more preferably 4.0 to 6.0. When the optical concentration is 2.0 or more, it is possible to suppress the deterioration of the display quality of the display device such as suppressing the contrast deterioration.

In addition, the optical density here means an ISO Visual transmission optical density. As a measuring instrument which can be used for the measurement of the ISO Visual transmission optical density, SAKATA INX ENG. And X-Rite 361T (V) manufactured by CO., LTD.

In addition, it is preferable that the black matrix has a line width (length in the direction orthogonal to the black matrix longitudinal direction sandwiched between the colored patterns) of 5 to 30 µm from the viewpoint of ensuring the brightness by high aperture ratio. The thickness of the black matrix (the length in the substrate normal direction of the black matrix) is preferably 0.2 to 2.0 µm from the viewpoint of reducing the ridge of the overlapping portion where the black matrix and the coloring pattern overlap (preferably 0.5 µm or less). More preferably, it is 0.2-1.5 micrometers, More preferably, it is 0.5-1.2 micrometers. Within this thickness range, the irregularities of the substrate on which the black matrix is installed, that is, the level difference between the formation region and the non-formation region of the black matrix are properly maintained so that a coloring pattern (colored pixel) such as RGB can be formed thereon after the black matrix is formed. Even when high precision can be formed.

Photosensitive deep color composition layer forming process

In this step, the photosensitive deep color composition is applied and then prebaked to form a photosensitive deep color composition layer on the substrate.

Examples of the substrate that can be used in the present step include alkali-free glass, soda glass, pyrex (registered glass), quartz glass, and the like having a transparent conductive film attached thereto or a photoelectric conversion element used in a solid state imaging device. Substrates such as silicon substrates. Plastic substrates are also possible. These substrates first form a black matrix in a lattice form or the like so as to isolate each pixel, and colored pixels are formed in empty portions of the lattice.

Furthermore, on these board | substrates, you may form a primer layer in order to improve the adhesion of an upper layer, to prevent the spread of a substance, or to planarize a board | substrate surface. It is preferable that a board | substrate is large (approximately 1 side or more 1m or more) from the point which exhibits the effect of this invention more.

As a method of forming a photosensitive deep color composition layer on a board | substrate, there exists a method of providing a photosensitive deep color composition by application | coating etc., for example on a board | substrate.

As a method of applying the photosensitive rich color composition on the substrate, various application methods such as a slit coater coating method, a spinner coating method, an inkjet method, a rotary coating method, a cast coating method, a roll coating method, and a screen printing method can be applied. Among them, the slit coater coating method and the spinner coating method are preferable in view of precision and speed.

60-140 degreeC is preferable and, as for the prebaking temperature of the photosensitive deepening composition layer formed on a board | substrate, 80-120 degreeC is more preferable. 30-300 second is preferable and, as for a prebaking time, 80-200 second is more preferable.

Although the thickness (for example, application | coating thickness) at the time of providing a photosensitive deepening composition on a board | substrate is adjusted suitably according to the design value of the thickness of the black matrix to form, generally 0.2-2.2 micrometers is preferable, and 0.2-1.6 micrometers It is more preferable that it is and it is most preferable that it is 0.5-1.3 micrometer.

Exposure process

In an exposure process, the photosensitive deepening composition layer formed in the said photosensitive deepening composition layer forming process is exposed through a predetermined | prescribed mask pattern, and patterning (only negatively irradiated coating film part is hardened). Especially as ultraviolet rays which can be used in exposure, ultraviolet rays, such as g line | wire, h line | wire, i line | wire, are used preferably. 5-500 mJ / cm <2> is preferable, 10-300 mJ / cm <2> of an irradiation amount is more preferable, and 10-200 mJ / cm <2> is the most preferable.

The exposure machine may be a proxy meter exposure machine, a mirror projection system, or a stepper system.

Development Process

Subsequently, by performing an alkali development process, when the photosensitive deepening composition is negative, for example, the tailings irradiation part in the said exposure can be eluted in aqueous alkali solution, and only the photocured part can be left.

As the developing solution, an organic alkali developing solution, an inorganic alkaline developing solution or a mixture thereof is used.

As an alkali chemicals used for a developing solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium Organic alkaline compounds such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the like; Alkaline aqueous solution diluted with pure water so that it may become 10 mass%, Preferably it is 0.01-1 mass% is used suitably as a developing solution. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes (rinses) with pure water after image development.

Moreover, the black matrix formation process in this invention may include the process of hardening the formed black matrix by exposure as needed before the baking (post-baking) process after the said development process.

[Coloring Pattern Forming Step]

In the present invention, in the coloring pattern forming step, after the photosensitive coloring composition is coated on the substrate on which the photosensitive rich composition layer (black matrix) after baking is formed, prebaking is performed to form a photosensitive coloring composition layer (photosensitive Coloring composition layer forming step), exposing the photosensitive coloring composition layer (color layer exposure step), developing the photosensitive coloring composition layer after exposure (color layer developing step), and baking the developed photosensitive coloring composition layer ( Colored layer baking process) and a coloring pattern is formed so that the distance in the width direction of the black matrix of the overlap part which overlaps with the said black matrix after baking may be 1.0-12 micrometers. In addition to each said process, a coloring pattern formation process may further provide another process as needed.

Photosensitive coloring composition layer forming process

In the photosensitive coloring composition layer formation process, after apply | coating the photosensitive coloring composition on the board | substrate with which the photosensitive deepening composition layer (black matrix) after baking is formed, it prebakes and forms a photosensitive coloring composition layer.

As a method of forming a photosensitive coloring composition layer on a board | substrate with a black matrix, the same method as the method of forming a photosensitive deepening composition layer on a board | substrate, ie, a coating method, can be used.

Especially, the method of apply | coating the photosensitive coloring composition on the whole board | substrate with a black matrix by the slit coater coating method or the spinner coating method is preferable from a viewpoint of a precision and a speed.

60-140 degreeC is preferable and, as for the prebaking temperature of the photosensitive coloring composition layer formed on a board | substrate, 80-120 degreeC is more preferable. 30-300 second is preferable and, as for a prebaking time, 80-200 second is more preferable.

0.5-3.0 micrometers is preferable and, as for the layer thickness of the photosensitive coloring composition layer, in order to acquire sufficient color reproduction area | region and to obtain sufficient brightness of a panel, it is more preferable that it is the range of 1.0-2.5 micrometers.

Colored layer exposure process

In the colored layer exposure step, the photosensitive coloring composition layer is exposed.

The exposure process of the photosensitive coloring composition layer can be performed similarly to the exposure process of the photosensitive deepening composition layer. When forming a multi-colored coloring pattern, it can expose every color through the predetermined mask pattern of each color, and can pattern (cure in the case of negative type) the photosensitive coloring composition layer of each color irradiated with light.

Colored layer development process

In the colored layer developing step, the photosensitive coloring composition layer after exposure is developed.

The developing process of the photosensitive coloring composition layer after exposure can perform the operation similar to the operation described in description of the developing process of the photosensitive deepening composition layer, and can use the developing solution demonstrated about the said developing process suitably.

Colored layer baking process

In the colored layer baking step, the developed photosensitive coloring composition layer is baked.

The method of baking the photosensitive coloring composition layer after image development can use the method similar to the baking process which bakes the photosensitive deepening composition layer mentioned above.

In addition, when forming the coloring pattern of multiple colors, such as RGB tricolor, the formation, exposure, image development, and baking cycle of the photosensitive coloring composition layer may be repeated by a desired number of colors, and the formation and exposure of the photosensitive coloring composition layer for each color is carried out. And all of the color components may be baked last after the development. Thereby, the color filter provided with the colored pixel which consists of a black matrix and a desired color is produced.

Next, the photosensitive coloring composition and the photosensitive deepening composition used for the manufacturing method of the color filter of this invention are demonstrated in detail.

<Photosensitive coloring composition>

The photosensitive coloring composition used for coloring pattern formation of the color filter of this invention is a radiation sensitive composition (for example, the radiation sensitive composition hardened | cured with light in the case of a negative type), (A-1) a coloring agent, (B ) It is preferable to contain a binder polymer, a (C-1) polymeric compound, (D) photoinitiator, and (E) solvent, and may further contain other additives, such as a polymer dispersing agent and surfactant as needed. .

-(A-1) colorant-

The colorant can be suitably selected from dyes and pigments, and the pigment used as the colorant may be either an inorganic pigment or an organic pigment, but it is preferable to use one having a small particle size as much as possible, considering that it is preferable to have a high transmittance. It is preferable that an average particle size is 10-100 nm, More preferably, it is the range of 10-50 nm. In the photosensitive coloring composition used in the present invention, pigment dispersibility and dispersion stability are improved even when the size of the colorant is small by using the polymer dispersant described later. Thus, even when the thickness is thin, colored pixels excellent in color purity can be formed. have.

Examples of inorganic pigments that can be used as colorants for forming colored patterns (colored pixels) include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, and magnesium And metal oxides such as chromium, zinc and antimony, and complex oxides of the above metals.

As the organic pigment, for example,

C.I. Pigment yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment orange 36, 38, 43, 71;

C.I. Pigment red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment violet 19, 23, 32, 37, 39;

C.I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment green 7, 36, 37;

C.I. Pigment brown 25, 28;

C.I. Pigment black 1, and the like.

Although it does not specifically limit in this invention, The following pigment is more preferable.

C.I. Pigment yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;

C.I. Pigment orange 36, 71;

C.I. Pigment red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;

C.I. Pigment violet 19, 23, 37;

C.I. Pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment green 7, 36, 37;

These organic pigments can be used individually or in combination in order to raise color purity. The specific example of a combination is shown below.

For example, as the pigment for red phase (R), anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or one or more thereof, bis azo yellow pigments, isoindolin yellow pigments, and quinophthalone yellows A mixture of a pigment or a perylene-based red pigment can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red 254 is mentioned as a diketopyrrolopyrrole pigment. The mixture of CI pigment yellow 139 is preferable at the point of color reproducibility. The mass ratio of the red pigment and the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing the difference from the NTSC target color. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. In addition, in the case of the combination of red pigments, it can adjust to chromaticity.

As the pigment for the green phase (G), a halogenated phthalocyanine pigment alone or a mixture of this and a bis azo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment can be used. . For example, examples of CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow 185 Mixing is preferred. The mass ratio of the green pigment and the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing the difference from the NTSC target color. As mass ratio, the range of 100: 30-100: 120 is especially preferable.

As a pigment for blue phase (B), a phthalocyanine type pigment can be used individually or it can use the mixture of this and a dioxadine type purple pigment. For example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 is preferred. As for the mass ratio of a blue pigment and a purple pigment, 100: 0-100: 50 are preferable, More preferably, it is 100: 5-100: 30.

As content of the (A-1) coloring agent (pigment) in the photosensitive coloring composition layer used for this invention, 25-75 mass% is preferable with respect to the total solid (mass) of the said composition, and 32-70 mass% is more desirable. (A-1) When content of a coloring agent (pigment) is in the said range, color density is enough and it is effective also to ensure the outstanding color characteristic.

(B) binder polymer

It is preferable that the said photosensitive coloring composition of this invention contains a binder polymer for the purpose of the improvement of a film | membrane characteristic, a development characteristic provision, etc. The following alkali-soluble resin can be used as a binder polymer.

Alkali-soluble resins used in the present invention are linear organic polymers, preferably groups which promote alkali solubility in molecules (preferably acrylic copolymers, styrene-based copolymers) (eg, carboxyl groups, phosphoric acid groups, It can select suitably from alkali-soluble resin which has a sulfonic acid group, a hydroxyl group, etc.).

More preferable examples of the alkali-soluble resin include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, and Japanese Patent Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers as described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 , Acrylic copolymers such as crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acid cellulose derivatives having a carboxylic acid in the side chain, and an acid anhydride added to a polymer having a hydroxyl group. Can be mentioned.

The acid value is preferably 10 to 200 mg KOH / g, preferably 30 to 180 mg KOH / g, more preferably 50 to 150 mg KOH / g.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is suitable especially. As another monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atoms of the alkyl group and the aryl group may be substituted with a substituent.

The alkyl (meth) acrylate and aryl (meth) acrylates Examples of ^{_{CH 2 = C (R 1)}} (COOR 3) [wherein, R ¹ is a hydrogen atom or a C1-5 alkyl group, R ³ is C 1 Or an alkyl group or an aralkyl group having 6 to 12 carbon atoms.] Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl ( Metha) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl ( Meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. Field Can be.

Moreover, the resin which has a polyalkylene oxide chain in a molecular side chain is also preferable. As said polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or these combination can also be used, The terminal is a hydrogen atom or a linear or branched alkyl group.

1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Examples of the acrylic copolymer having a polyalkylene oxide chain in these side chains include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. And compounds containing an alkyl-blocked terminal OH group such as methoxy polyethylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, methoxy poly (ethylene glycol-propylene glycol) mono (meth) acrylic It is an acrylic copolymer which makes a rate etc. a copolymerization component.

As the vinyl compound, CH ₂ = CR ¹ R ² (wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms). Specifically, styrene, (alpha) -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, etc. are mentioned.

The other monomer which can be copolymerized can be used individually by 1 type or in combination of 2 or more type. Among these, a multipart copolymer consisting of benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomers is particularly suitable.

As described above, the acrylic resin has an acid value in the range of 20 to 200 mgKOH / g. If the acid value is 200 or less, the acrylic resin does not become too soluble in alkali so that the development proper range (developing latitude) can be prevented from narrowing. On the other hand, if it is 20 or more, since the solubility to alkali is unlikely to be small, prolongation of development time can be prevented.

In addition, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of acrylic resin is 2,000-100,000 in order to implement | achieve the viscosity range which is easy to use in the process of apply | coating a photosensitive coloring composition, and to ensure film strength. Preferably, it is 3,000-50,000 more preferably.

Moreover, in order to improve the crosslinking efficiency of the photosensitive coloring composition in this invention, you may use together resin which has a polymeric group in alkali-soluble resin alone or with alkali-soluble resin which does not have a polymeric group, and an aryl group, (meth) acryl Polymers containing a group, an aryloxyalkyl group and the like in the side chain are useful. Alkali-soluble resin which has a polymerizable double bond can develop in alkaline developing solution, and is equipped with photocurability and heat changeability. Examples of the polymers containing these polymerizable groups are shown below, but are not limited as long as they contain unsaturated bonds between alkali-soluble groups such as COOH groups and OH groups and carbon-carbon in one molecule.

(1) urethane-modified polymerizable obtained by reacting an isocyanate group with an OH group in advance to leave one unreacted isocyanate group, and also by reaction of a compound containing at least one (meth) acryloyl group and an acrylic resin containing a carboxyl group. Double bond-containing acrylic resin,

(2) an unsaturated group-containing acrylic resin obtained by reaction of an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond together in a molecule,

(3) acid pendant epoxy acrylate resin,

(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.

Among the above, resins of (1) and (2) are particularly preferable.

As an example, the epoxy ring and carbon-carbon unsaturated which have reactivity with respect to an OH group in the copolymer of monomers, such as 2-hydroxyethyl acrylate which has an OH group, for example, methacrylic acid containing a COOH group, and acrylic or vinyl compounds copolymerizable with these, are carbon-unsaturated. The compound etc. which are obtained by making a compound (for example, compounds, such as glycidyl acrylate) which have a coupling group react can be used. In the OH group reaction, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can be used in addition to the epoxy ring.

Furthermore, saturated or unsaturated polybasic acid anhydrides are reacted with a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938. The reactants obtained can also be used.

As a compound which made alkali-solubilizing group, such as a COOH group, and carbon-to-carbon unsaturated group react, For example, DIANAL NR series (made by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.); VISCOAT R-264, KS RESIST 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.); CYCLOMER P series, PLACCEL CF200 series (all manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.); Ebecryl 3800 (product of DAICEL UCB Co., LTD.), Etc. are mentioned.

As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-30 mass% in the total solid of the photosensitive coloring composition layer, and 5-20 mass% is more preferable.

At the time of preparation of the photosensitive coloring composition, it is preferable to add the following epoxy resin further in addition to the said alkali-soluble resin as a binder polymer. As an epoxy resin, the compound which has two or more epoxy rings in a molecule | numerator, such as a bisphenol A type, a cresol noblock type, a biphenyl type, and an alicyclic epoxy compound, is mentioned.

For example, as bisphenol A, EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, and the like (above, Tohto Kasei Co., Ltd.), DENACOL EX-1101, EX-1102, EX-1103 (above, Nagase chemtex corporation), PLACCEL GL-61, GL-62, G101, G102 (or above, DICEL CHEMICAL INDUSTRIES , LTD. Products) and the like, and bisphenol F type and bisphenol S type epoxy resins similar to these may also be used.

Moreover, epoxy acrylates, such as Ebecryl 3700, 3701, 600 (above, DAICEL UCB Co., LTD.), Can also be used. As the cresol noblock type, EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei Co., Ltd.), DENACOL EM-125, etc. (from Nagase chemtex corporation) As an alicyclic epoxy compound, such as 3,5,3 ', 5'- tetramethyl- 4,4'- diglycidyl biphenyl as a biphenyl type, CELLOXIDE 2021, 2081, 2083, 2085, EPOLEAD GT-301, GT -302, GT-401, GT-403, EHPE-3150 (above, manufactured by DICEL CHEMICAL INDUSTRIES, LTD.), Santoto ST-3000, ST-4000, ST-5080, ST-5100, etc. (above, Tohto Kasei Co ., Ltd.), Epiclon 430, 673, 695, 850S, 4032 (above, manufactured by DIC Corporation), and the like. 1,1,2,2-tetrakis (p-glycidyl oxyphenyl) ethane, tris (p-glycidyl oxyphenyl) methane, triglycidyl tris (hydroxyethyl) isocyanurate, o In addition to phthalic acid diglycidyl ester and telephthalic acid diglycidyl ester, amine type epoxy resins EPOTOHTO YH-434, YH-434L, and glycidyl esters modified with dimer acid in the skeleton of bisphenol A type epoxy resins can also be used. Can be.

Especially, "molecular weight / number of epoxy rings" is 100 or more, and 130-500 are more preferable. If the "molecular weight / number of epoxy rings" is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient, resulting in insufficient reliability or poor flatness.

Specific preferred compounds include EPOTOHTO YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, PLACCEL GL-61, GL-62, 3,5,3 ', 5'-tetramethyl-4,4 -Diglycidyl biphenyl, CELLOXIDE 2021, 2081, EPOLEAD GT-302, GT-403, EHPE-3150, etc. are mentioned.

-(C-1) polymeric compound-

It is preferable that the photosensitive coloring composition used for this invention contains the (C-1) polymeric compound.

The polymerizable compound which can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably at least two, terminal ethylenically unsaturated bonds. Such a compound group is well known in the industrial field, and in the present invention, these compounds can be used without particular limitation. These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its ester, and amide are mentioned, Preferably it is unsaturated Esters of carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds are used. Moreover, addition reaction product of unsaturated carboxylic ester or amides which have nucleophilic substituents, such as a hydroxyl group, an amino group, and a mercapto group, and monofunctional or polyfunctional isocyanate, or epoxy, and monofunctional or polyfunctional carbon The dehydration condensation product of an acid, etc. are also used suitably. Moreover, the addition reaction product of unsaturated carboxylic ester or amides which have electrophilic substituents, such as an isocyanate group and an epoxy group, and monofunctional or polyfunctional alcohols, amines, and thiols, and leaving substituents, such as a halogen group and a tosyloxy group, Substituted reactants of unsaturated unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines and thiols are also suitable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

Specific examples of ester monomers of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene glycol diacrylate. Acrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate Sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, and the like.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacryl Laterate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipenta Erythritol hexa methacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxy Ethoxy) phenyl] dimethylmethane and the like.

As itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaco Nate and the like. Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include, for example, aliphatic alcohol esters described in Japanese Patent Application Laid-Open No. 51-47334, Japanese Patent Application Laid-Open No. 57-196231, Japanese Patent Application Laid-Open No. 59-5240, and Japanese Patent Publication No. 59- The thing which has the aromatic skeleton of Unexamined-Japanese-Patent No. 5241, Unexamined-Japanese-Patent No. 2-226149, the thing containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are used suitably. In addition, the ester monomer mentioned above can also be used as a mixture.

Moreover, as an example of the amide monomer of an aliphatic polyhydric amine compound and unsaturated carboxylic acid, methylene bis- acrylamide, methylene bis-methacrylamide, 1, 6- hexamethylene bis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylene triamine trisacrylamide, xylene bis-acrylamide, xylene bis-methacrylamide and the like. As an example of another preferable amide monomer, what has a cycloxylene structure as described in Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Also suitable are urethane-based addition polymerizable compounds produced using addition reactions of isocyanates and hydroxyl groups, and specific examples thereof include poly having two or more isocyanate groups in one molecule, for example, described in JP-A-48-41708. The vinylurethane compound etc. which contain two or more polymerizable vinyl groups in the molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (V) to an isocyanate compound are mentioned.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (V)

(Where R ⁴ And R ⁵ each independently represent H or CH _3. )

Furthermore, urethane acrylates and Japanese Patent Publications No. 58-49860, such as those described in Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-open No. Hei 2-16765. Also suitable are urethane compounds having an ethylene oxide-based skeleton described in JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418. In addition, addition polymerizable compounds having an intramolecular amino structure or sulfide structure described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 are used. By doing this, the photopolymerizable composition which is extremely excellent in the photosensitive speed can be obtained.

Other examples include polyester acrylates, epoxy resins and the like as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates, such as the epoxy acrylate which made (meth) acrylic acid react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, and the vinyl force of Unexamined-Japanese-Patent No. 2-25493 are mentioned. Phonic acid compounds and the like. Moreover, in some cases, the structure containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-22048 is used preferably. Furthermore, Japanese Adhesion Association vol. 20, No. 7, 300 to 308 pages (1984) can also be used as photocurable monomers and oligomers.

About these polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a final sensing material. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in many cases, bifunctional or more is preferable. In addition, in order to raise the intensity | strength of a coloring image part, ie, the photosensitive coloring composition layer, a trifunctional or more functional thing is good, and also of other functional water and other polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, a styrene type compound, a vinyl ether type compound) It is also effective to adjust both the sensitivity and the intensity by using the same. It is preferable to use the compound containing 2 or more of (meth) acrylic acid ester structure from a viewpoint of hardening sensitivity, It is more preferable to use the compound containing 3 or more, It is preferable to use the compound containing 4 or more Most preferred. Moreover, it is preferable to contain an EO modified body from a hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part strength.

In addition, the selection and use of the addition polymerization compound are also important factors in terms of compatibility and dispersibility with other components (eg, binder polymer, initiator, colorant (pigment, dye, etc.)) in the photosensitive coloring composition layer. However, compatibility may be improved by using 2 or more types together. Moreover, a specific structure can also be selected for the purpose of improving adhesiveness with a board | substrate.

In view of the above, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, and tetraethylene glycol diacryl Latex, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , Sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, dipentaerythritol hexaacrylate EO modified, etc. As a commercial item, urethane oligomer UAS-10, UAB-140 (made by NIPPON PAPER GROUP, Inc.), DPHA (made by NIPPON KAYAKU Co., Ltd.), UA-306H, UA-306T, UA-306I , AH-600, T-600, and AI-600 (manufactured by KYOEISHA Co., Ltd.) are preferred.

In particular, bisphenol A diacrylate EO modified substance, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, Pentaerythritol tetraacrylate EO modifier, dipentaerythritol hexaacrylate EO modifier, and the like are commercially available products such as DPHA (manufactured by NIPPON KAYAKU Co., Ltd.), UA-306H, UA-306T, UA-306I, and AH-600. , T-600 and AI-600 (manufactured by KYOEISHA Co., Ltd.) are more preferable.

It is preferable that content of (C-1) polymeric compound is 5-55 mass% in all solid content in the photosensitive coloring composition layer of this invention, It is more preferable that it is 10-50 mass%, It is 15-45 mass% More preferred.

-(D) photoinitiator-

It is preferable that the photosensitive coloring composition of this invention contains the (D) photoinitiator.

The said photoinitiator is a compound which decomposes | disassembles by light, and starts and accelerates superposition | polymerization of the said (C-1) polymeric compound, It is preferable to have absorption in the area | region of wavelength 300-500 nm. In addition, the said photoinitiator can be used individually or in combination of 2 or more types.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metalocene compounds, Hexaaryl biimidazole compound, an organoboric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, an acyl phosphine (oxide) compound is mentioned.

As an organic halogenated compound, specifically Wakabayashi et al., "Bull Chem. Soc Japan '' 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A The compounds described in JP-A-63-70243, JP-A-63-298339, MP Hutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970), and the like. Substituted oxazole compounds and s-triazine compounds.

More suitably as s-triazine compounds, s-triazine derivatives in which one or more mono, di or tri halogen-substituted methyl groups are bonded to the s-triazine ring, specifically, for example 2,4,6-tris (monochloro Methyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4 , 6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chloro phenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine , 2-styryl-4,6-bis (trickle) Rommethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-nathoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6 -Tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s -Triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. are mentioned.

As the oxydiazole compound, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4- Oxodiazole, etc. may be mentioned.

Examples of the carbonyl compound include benzophenone, Michler's ketone, 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxy benzophenone. Phenone derivatives, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenyl propane, 1-hydroxy -1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 '-(methylthio) phenyl) -2- Morpholino-1-propaneone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, Acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone and 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, thioxanthone, 2-ethyl thioke Santone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, Thioxanthone derivatives, such as 2, 4- diethyl thioxanthone and 2, 4- diisopropyl thioxanthone, benzoic acid ester derivatives, such as p-dimethylamino benzoate ethyl and p-diethylaminobenzoic acid ethyl, etc. are mentioned. have.

Benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl ethyl acetal, etc. are mentioned as a ketal compound.

Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate and the like.

Acridine compounds include 9-phenyl acridine, 9-pyridyl acridine, 9-pyridinyl acridine, 1,2-di (9-acridinyl) ethane, 1,3-di (9 -Acridinyl) propane, 1,4-di (9-acridinyl) butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1 , 7-di (9-acridinyl) heptane, 1,8-di (9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-arc And di (9-acridinyl) alkanes such as 1,11-di (9-acridinyl) undecane and 1,12-di (9-acridinyl) dodecane. .

Examples of the organic peroxide compound include trimethyl cyclohexanone peroxide, acetyl acetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethyl cyclohexane, 1,1-bis (tert-butyl Peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butylhydro peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2 , 5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert -Butyl peroxy) hexane, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropylperoxy dicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl Peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butylperoxyace , Tert-butylperoxy pivalate, tert-butylperoxy neodecanoate, tert-butylperoxyoctanoate, tert-butylperoxy laurate, 3,3 ', 4,4'-tetra- ( t-butylperoxy carbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-hexylperoxy carbonyl) benzophenone, 3,3', 4,4'-tetra- (p- Isopropyl cumylperoxycarbonyl) benzophenone, carbonyl di (t-butylperoxy dihydrogen 2 phthalate), carbonyl di (t-hexylperoxy dihydrogen 2 phthalate), and the like.

As an azo compound, the azo compound etc. which were described in Unexamined-Japanese-Patent No. 8-108621 are mentioned, for example.

Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenyl coumarin, 3-chloro-5-diethylamino-((s-triazine-2 -Yl) amino) -3-phenyl coumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenyl coumarin, etc. are mentioned.

Examples of azide compounds include the organic azide compounds described in US Pat. No. 2848328, US Pat. No. 2852379, and US Pat. No. 2940853, 2,6-bis (4-azidebenzylidene) -4-ethyl cyclohexa. Rice (BAC-E) etc. are mentioned.

As the metallocene compound, Japanese Patent Laid-Open No. 59-152396, Japanese Patent Laid-Open No. 61-151197, Japanese Patent Laid-Open No. 63-41484, Japanese Patent Laid-Open No. 2-249, and Japanese Patent Laid-Open No. 2 Various titanocene compounds described in -4705 and Japanese Patent Laid-Open No. 5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6- Difluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenni-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6 -Trifluoropheni-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheni-1-yl, di-cyclopentadienyl-Ti-bis-2 , 3,4,5,6-pentafluoropheni-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluoropheni-1-yl, di-methylcyclopentadienyl -Ti-bis-2,4,6-trifluoropheni-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetra Fluoropheni-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheni-1-yl, Japanese Patent Laid-Open No. 1-304453, Japan The iron-arene complex described in Unexamined-Japanese-Patent No. 1-52109 is mentioned.

Examples of the hexaaryl biimidazole compound include various compounds described in each specification, such as Japanese Patent Application Laid-open No. Hei 6-29285, US Patent No. 3,479,185, US 4,311,783, US 4,622,286, and specifically, 2,2 '. -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-bromophenyl)) 4,4', 5,5'-tetra Phenyl biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenyl ratio Imidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5 , 5'-tetraphenyl biimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, etc. are mentioned.

As an organic borate compound, Unexamined-Japanese-Patent No. 62-143044, Unexamined-Japanese-Patent No. 62-150242, Unexamined-Japanese-Patent No. 9-188685, Unexamined-Japanese-Patent No. 9-188686, Unexamined-Japanese-Patent No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, and Kunz, Martin "Rad Organic borate described in Tech '98. Proceeding April 19-22, 1998, Chicago ", Japanese Patent Application Laid-Open No. 6-157623, Japanese Patent Application Laid-Open No. 6-175564, Japanese Patent Publication No. 6-175561 The organoboron sulfonium complexes described or organoboron oxosulfonium complexes, the organic boron iodonium complexes described in JP-A-6-175554, and JP-A-6-175553, JP-A-9-188710 Organoboron phosphonium complex described in Japanese Patent Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785, Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527, Japanese Patent Laid-Open No. 7-292014, and the like. An organoboron transition metal coordination complex etc. are mentioned as a specific example.

As a disulfone compound, the compound etc. which are described in Unexamined-Japanese-Patent No. 61-166544, Unexamined-Japanese-Patent No. 2002-328465, etc. are mentioned.

Examples of oxime ester compounds include JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and the compounds described in Japanese Patent Application Laid-Open No. 2000-66385, Japan The compound of Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2004-534797, etc. are mentioned. As a specific example, Ilgacua OXE-01 of the Ciba Specialty Chemicals product, OXE-02, etc. are preferable.

As the onium salt compound, for example, S. I. Schlesinger, Photogr. Sci. Diazonium salts described in Eng., 18,387 (1974), TS Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, and US patents. Phosphonium salts described in the specifications of No. 4,069,055, 4,069,056, European Patent No. 104,143, US Patent No. 339,049, and Japanese Patent Publication No. 2-150848 And iodonium salts described in Japanese Patent Application Laid-Open No. 2-296514.

The iodonium salt which can be preferably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it is preferable that two or more iodonium salts are substituted with an electron-donating group such as an alkyl group, an alkoxy group or an aryloxy group. Moreover, as a form of another preferable sulfonium salt, the iodonium salt etc. which one substituent of a triaryl sulfonium salt has coumarin and anthraquinone structure, and has absorption in 300 nm or more are preferable.

Examples of sulfonium salts that can be suitably used in the present invention include European Patent No. 370,693, Patent 390,214, Patent 233,567, Patent 297,443, Patent 297,442, Patent 4,933,377, Patent 161,811, The sulfonium salts described in each of the specifications of 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, 2,904,626, 3,604,580, 3,604,581 It is preferable that it can be substituted by the electron-withdrawing group from the stability point of stability. As the electron withdrawing group, the one having a Hammett value greater than zero is preferable. Preferred electron withdrawing groups include halogen atoms, carboxylic acids and the like.

Moreover, as another preferable sulfonium salt, the sulfonium salt which one substituent of a triaryl sulfonium salt has a coumarin and anthraquinone structure, and has absorption in 300 nm or more is mentioned. As another preferable sulfonium salt, the sulfonium salt which triaryl sulfonium salt has an allyloxy group and an arylthio group as a substituent and has absorption in 300 nm or more is mentioned.

As onium salt compounds, J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al, J. Polymer Sci., Polymer Chem. Selenium salts described in Ed., 17, 1047 (1979), C. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p. Onium salts, such as the arsonium salt of 478, Tokyo, Oct. (1988), etc. are mentioned.

As an acyl phosphine (oxide) compound, Ilgacua 819, Darocua 4265, Darocua TPO, etc. which are a Ciba Specialty Chemicals product are mentioned.

(D) As a photoinitiator, a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, the acyl phosphine type compound, a phosphine oxide type compound, a metallo from a viewpoint of exposure sensitivity. Sen compound, oxime compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyl Preferred are compounds selected from the group consisting of oxadiazole compounds and 3-aryl substituted coumarin compounds.

More preferably, trihalomethyl triazine compound, α-amino ketone compound, acyl phosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, At least one compound selected from the group consisting of an acetophenone compound, a trihalomethyl triazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is most preferred. .

It is preferable that content of (D) photoinitiator is 0.1-20 mass% with respect to all solid content in the photosensitive coloring composition layer, More preferably, it is 0.5-15 mass%, Especially preferably, it is 1-10 mass%. In this range, good sensitivity and pattern formability can be obtained.

-(E) solvent-

The photosensitive coloring composition used for this invention can be prepared generally using a solvent.

Examples of the solvent include esters such as ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxy acetate, ethyl oxy acetate, butyl oxy acetate, methyl methoxy acetate, methoxy ethyl acetate, methoxy acetate, ethoxy methyl acetate, ethyl ethoxy acetate, and methyl 3-oxypropionate, 3-oxy 3-oxypropionic acid alkyl esters such as ethyl propionate (for example, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.), methyl 2-oxypropionate, 2-oxypropionic acid alkyl, such as 2-oxyethyl propionate and 2-oxypropionic acid propyl Teres such as methyl 2-methoxy propionate, 2-methoxy ethylpropionate, 2-methoxy propyl propionate, methyl 2-ethoxy propionate, ethyl 2-ethoxy propionate, methyl 2-oxy-2-methyl propionate, 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, etc.), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetate methyl, acetoacetate Ethyl, methyl 2-oxobutanoic acid, ethyl 2-oxobutanoic acid, 1,3-butanediol diacetate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether , Diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether Cate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tripropylene glycol mono n-butyl ether, tripropylene glycol methyl ether acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like;

Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, aromatic hydrocarbons such as toluene, xylene and the like.

Among these, as mentioned above, it is preferable that it is a solvent (containing 30-70 mass%) of boiling point 100 degreeC or more as mentioned above, and especially propylene glycol monomethyl ether acetate, cyclohexanone, methyl ethyl ketone, and 3-ethoxy ethyl propio It is preferable that it is at least 1 sort (s) chosen from a nate.

A solvent may be used in combination of 2 or more type other than using independently.

-Other additives-

Moreover, in addition to the said component, various well-known additives can further be used for the photosensitive coloring composition used for this invention according to the objective.

Hereinafter, such an additive is demonstrated.

(Dispersant)

It is preferable that the photosensitive coloring composition in this invention contains a polymeric dispersing agent. This polymer dispersing agent is resin which has a weight average molecular weight in the range of 3,000-100,000. Moreover, it is preferable that acid value is 20-300 mg / g. Such specific polymer dispersing agent may be called "dispersion resin" below.

The dispersing resin in this invention can function as a dispersing agent of the pigment quoted as said (A-1) colorant, or a dispersing agent of a light shielding agent (pigment for black matrix formation) in the photosensitive deepening composition for formation of the black matrix mentioned later. Compound.

Since dispersion resin needs to have specific acid value, it is preferable that it is a high molecular compound which has an acidic group.

Examples of the polymer skeleton of the polymer compound include polymers of vinyl monomers, copolymers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified or copolymers thereof [e.g., polyethers / Polyurethane copolymer, copolymer of a polymer of polyether / vinyl monomer, and the like (random copolymer, block copolymer, graft copolymer may be any), etc.] one or more selected from the group consisting of More preferably, at least one selected from the group consisting of polymers of vinyl monomers, copolymers, ester polymers, ether polymers, urethane polymers, and modified or copolymers thereof, more preferably polymers of vinyl monomers Copolymers are particularly preferred.

Moreover, as a method of introducing an acidic group into the above-mentioned polymer skeleton, the method of copolymerizing the monomer containing an acidic group when superposing | polymerizing the said polymer skeleton, and also the method of introduce | transducing the said polymer skeleton by polymer reaction after superposition | polymerization are mentioned, for example. have.

Examples of the monomer containing an acidic group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, and phosphoric acid mono ( And monomers obtained by reacting an alcoholic hydroxyl group-containing monomer such as meta) acryloyl ethyl ester or 2-hydroxyethyl methacrylate with cyclic acid anhydrides such as maleic anhydride and phthalic anhydride.

In addition, the high molecular compound which has an acidic group may be comprised by copolymerizing a vinyl monomer component.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) acrylamide, Vinyl ether, ester of vinyl alcohol, styrene, (meth) acrylonitrile, etc. are preferable.

As said "acidic group", a carboxylic acid group, a sulfonic acid group, a monosulfate ester group, a phosphoric acid group, a monophosphate ester group, a boric acid group is mentioned as a preferable example, for example, A carboxylic acid group, a sulfonic acid group, a monosulfate ester group, a phosphoric acid group, Monophosphate ester groups are more preferred, and carboxylic acid groups, sulfonic acid groups and phosphoric acid groups are particularly preferred.

It is also preferable to contain a group having a basic nitrogen atom in order to improve dispersibility. The group having the basic nitrogen atom is, for example, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , or -NR ⁹ R ¹⁰ ; wherein R ⁸ , R ⁹ and R ¹⁰ are each independently 1 to 20 carbon atoms. An alkyl group, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.), A guanidyl group represented by the following formula (a1), or an amidinyl group represented by the following formula (a2) Can be mentioned.

R ¹¹ and R ¹² in the formula (a1) each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

R ¹³ and R ¹⁴ in the formula (a2) each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , or -NR ⁹ R ¹⁰ ; wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group. .), A guanidyl group represented by the general formula (a1) [wherein R ¹¹ and R ¹² each independently represent an alkyl group, a phenyl group or a benzyl group having 1 to 10 carbon atoms; Amidinyl groups (R ¹³ and R ¹⁴ in the formula (a2) each independently represent an alkyl group, a phenyl group or a benzyl group having 1 to 10 carbon atoms.) And the like, and a hydrogen atom and 0 to 20 sulfur atoms. The group which consists of these is included, These may be unsubstituted or may have a substituent further.

(Other dispersants)

The photosensitive coloring composition used for this invention can also use together a conventionally well-known dispersing agent (pigment dispersing agent) other than a dispersion resin.

Known dispersants (pigment dispersants) include polymer dispersants [e.g., polyamide amines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers], And polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanolamines, pigment derivatives, and the like.

Polymeric dispersants can be classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure thereof.

Polymeric dispersants act to adsorb to the surface of the pigment to prevent reagglomeration. Therefore, the terminal modified | denatured polymer | macromolecule, graft-type polymer, and block polymer which have anchor site | part on a pigment surface are mentioned as a preferable structure. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

As a specific example of the known dispersant (pigment dispersant) which can be used in the present invention, BYK-Chemie GmbH `` Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (Polymer copolymer), EFKA products `` EFKA 4047, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”, Ajinomoto Fine-Techno Co., Inc. Products `` AJISPER PB 821, PB 822 '', Kyoeisha Chemical Co., Ltd. Product "FLOWLEN TG-710 (urethane oligomer)", "POLYFLOW No. 50E, No. 300 (acrylic copolymer) ”, KUSUMOTO CHEMICALS, Ltd. Product "DISPARLON # 7004 (polyether ester), DA-703-50, DA-705, DA-725", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)" from KAO Corporation, "ACETAMIN" 86 (stearylamine acetate) ”, Lubrizol Japan Ltd. Products `` SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (grafted polymer) , NIKKO Chemicals Co., Ltd. A product "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", etc. are mentioned.

The above-mentioned well-known dispersing agent can be used in the range of 10-100 mass%, ie, 1 / 10-1 / 1 (equivalent amount) with respect to dispersion resin as needed.

(Surfactants)

Increasing the pigment concentration generally increases the thixotropy of the coating liquid, so that the thickness nonuniformity after the formation of the photosensitive coloring composition layer (color layer coating film) is easily applied by applying or transferring the photosensitive coloring composition onto the substrate. Moreover, especially in the formation of the photosensitive coloring composition layer (color layer coating film) by the slit coating method, it is important to level the coating liquid for photosensitive coloring composition layer formation until drying, and to form the coating film of uniform thickness. For this reason, it is preferable to contain an appropriate surfactant in the said photosensitive coloring composition. As said surfactant, surfactant disclosed in Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a suitable thing.

As surfactant for improving applicability | paintability, a nonionic surfactant, a fluorine-type surfactant, a silicone type surfactant, etc. are added.

Examples of nonionic surfactants include polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers, and poly Nonionic surfactants, such as oxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, are preferable.

Specifically, Polyoxyalkylene glycol, such as polyoxyethylene glycol and polyoxypropylene glycol; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polystyrylated ether and polyoxyethylene noniphenyl ether; And nonionic surfactants such as polyoxyalkylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters.

Specific examples thereof include, for example, ADEKAPLURONIC Series, ADEKA NOL Series, TETRONIC Series (above, ADEKA Corporation), EMULGEN Series, RHEODOL Series (above, Kao Corporation), ELEMINOL Series, NONIPOL Series, OCTAPOL Series, DODECAPOL Series, NEWPOL Series (above, Sanyo Chemical Industries, Ltd.), PIONIN Series (above, TAKEMOTO OIL & FAT CO., Ltd.), NISSAN NONION Series (above, NOF CORPORATION). These commercially available can be used suitably. Preferable HLB value is 8-20, More preferably, it is 10-17.

As the fluorine-based surfactant, a compound having a fluoroalkyl or a fluoroalkylene group at any one or more of the terminal, main chain and side chain can be suitably used.

As a specific commercial item, for example, MEGAFAC EF142D, F172, F173, F176, F177, F183, 780, 781, R30, R08 (manufactured by DIC Corporation), FLUORAD FC-135, FC-170C, East FC-430, East FC-431 (manufactured by SUMITOMO 3M Limited), Surflon S-112, East S-113, East S-131, East S-141, East S-145, East S-382, East SC-101 , SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by ASAHI GLASS Co., Ltd.), Eftop EF 351, Copper 352, Copper 801, Copper 802 (JEMCO Inc.).

As a silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428, copper DC -57, copper DC-190 (above, from Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba silicones Product).

These surfactant is preferably 5 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the coating liquid for forming the photosensitive coloring composition layer. When the amount of the surfactant exceeds 5 parts by mass, surface roughness in coating drying tends to occur, and smoothness tends to deteriorate.

In addition, when promoting alkali solubility of an uncured part and improving developability of a photocurable composition, addition of organic carboxylic acid, Preferably low molecular weight organic carboxylic acid of molecular weight 1000 or less can be performed. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sveric acid, azelaic acid, sebacic acid, brassic acid, methyl malonic acid, ethyl malonic acid, dimethyl malonic acid, methyl succinic acid, tetramethyl succinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Phenyl acetic acid, phenoxy acetic acid, methoxy phenoxy acetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildenic acid, coumaric acid And other carboxylic acids such as umberic acid.

(Alkoxysilane Compound)

The alkoxysilane compound, especially a silane coupling agent, can be used for the photosensitive coloring composition used for this invention from a viewpoint of the adhesive improvement of a board | substrate.

The silane coupling agent preferably has an alkoxy silyl group as a hydrolyzable group chemically bondable with an inorganic material, and (meth) acryloyl, phenyl, mercapto, epoxy, which exhibit affinity by interaction or bond formation between organic resins. It is preferable that it is a silane, and it is more preferable that it is (meth) acryloyl propyl trimethoxysilane among these.

As addition amount at the time of using a silane coupling agent, it is preferable that it is the range of 0.2-5.0 mass% in the total solid in the photosensitive coloring composition layer used for this invention, and 0.5-3.0 mass% is more preferable.

(Notary sensitizer)

It is also preferable that the photosensitive coloring composition used for this invention contains a sensitizer as needed. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and the initiator to the active radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MR Sander et al., Journal of Polymer Society, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, and Japanese Patent JP-A-52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure The compound of 33825 etc. are mentioned, Specifically, a triethanolamine, p-dimethylamino benzoic acid ethyl ester, p-formyldimethylaniline, p-methylthio dimethylaniline, etc. are mentioned.

Other examples of the sensitizer include thiols and sulfides such as the thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent Publication No. The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercapto benzothiazole, 2-mercapto benzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) ) -Quinazoline, β-mercaptonaphthalene, and the like.

Other examples of the sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyl tin acetate, etc.) described in Japanese Patent Publication No. 48-42965, Japanese Patent Publication No. 55-34414 The hydrogen donor described in Unexamined-Japanese-Patent, the sulfur compound (for example, trithiane etc.) of Unexamined-Japanese-Patent No. 6-308727, etc. are mentioned.

As for content of these co-sensitizers, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the cure rate by the balance of polymerization growth rate and chain transfer, and the range of 1-25 mass% Is more preferable, and the range of 0.5-20 mass% is still more preferable.

(Polymerization inhibitor)

In the present invention, it is preferable to add a small amount of thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the compound having an ethylenically unsaturated double bond which is polymerizable during the production or storage of the photosensitive coloring composition.

Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3 -Methyl-6-t-butyl phenol), 2,2'-methylenebis (4-methyl-6-t-butyl phenol), N-nitrosophenyl hydroxyamine 1st cerium salt, etc. are mentioned.

As for the addition amount of a thermal polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass in the photosensitive coloring composition layer. Moreover, in order to prevent the inhibition of polymerization by oxygen, you may add higher fatty acid derivatives, such as behenic acid and behenic acid amide, and may make it localize on the surface of the photosensitive layer in the drying process after application | coating. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the whole composition.

(Plasticizer)

In addition, in this invention, in order to improve the physical property of the photosensitive coloring composition layer, you may add the inorganic filler, a plasticizer, the sensing agent which can improve the ink buildability of the photosensitive layer surface, etc.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine, and the like. 10 mass% or less can be added with respect to the total mass of the compound which has an ethylenically unsaturated double bond, and a binder.

By using the above-mentioned component, the photosensitive coloring composition in this invention hardens with high sensitivity, and storage stability is also favorable. Moreover, high adhesiveness to a board | substrate is shown. Therefore, the photosensitive coloring composition containing the said various components can be used suitably for a color filter.

<Photosensitive deep color composition>

It is preferable that the photosensitive deepening composition used for this invention contains (A-2) light-shielding agent, (B) binder polymer, (C-2) polymeric compound, (D) photoinitiator, and (E) solvent, and is necessary. According to the invention, other additives such as dispersants and surfactants may be contained.

(A-2) Shading Agent

Examples of the light-shielding agent (A-2) include carbon black, titanium black, metal fine particles, metal oxides, and fine particles of sulfides in addition to the colorant (A-1). Especially, carbon black which is excellent in the balance of light-shielding property and cost is especially preferable.

These are used individually or in combination of multiple types as needed. Examples thereof include carbon black alone, mixed organic pigments, combined use of carbon black and organic pigments, and the like.

As a light-shielding material, at least 2 or more types of pigments which shield a visible light region have been used together as a black coloring agent conventionally. These pigments include the pigments described in Japanese Patent Application Laid-Open Nos. 2005-17716, and the pigments described in Japanese Patent Laid-Open Nos. 2005-17521, and [0080] to [0088]. Formation is disclosed in Japanese Patent Laid-Open No. 7-271020 and the like.

In order to increase the light shielding effect, carbon black, titanium black, or graphite are suitable as light blocking materials in Japanese Patent Laid-Open Publication No. 2000-147240, Japanese Patent Laid-Open Publication 2000-143985, Japanese Patent Laid-Open Publication 2005-338328, and Japanese Patent Publication 2006-154849. Has been developed. In the present invention, carbon black is preferred as one of the light shielding materials from the viewpoint of light shielding properties and cost.

As an example of carbon black, pigment black 7 (carbon black) is preferable. As carbon black, it is MITSUBISHI RAYON Co., Ltd., for example. Carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, DIABLACK A, DIABLACK N220M, DIABLACK N234, DIABLACK I, DIABLACK LI, DIABLACK II, DIABLACK N339, DIABLACK SH, DIABLACK SHA, DIABLACK LH, DIABLACK H, DIABLACK HA, DIABLACK SF, DIABLACK N550M, DIABLACK E, DIABLACK G, DIABLACK R, DIABLACK N760M, DIABLACK LP; Evonic Degussa Japan Co., Ltd. Products Carbon Black Color Black FW200, Color Black FW2, Color Black FW1, Color Black FW18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Printex U, Printex V, Printex 140U, Printex 140V, Printex 35; Carbon Black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS 1400 from Carbot Corporation; Asahi Carbon Co., Ltd. Carbon black SUNBLACK 900, copper 910, copper 930, copper 960, copper 970 etc. of the product are mentioned. It is also preferable to coat these with a high molecular compound in order to increase the electrical resistance. The preferred size of single particles of these carbon blacks is 10 to 100 nm, more preferably 10 to 50 nm.

-(C-2) polymeric compound-

Although the (C-1) polymeric compound used in the said photosensitive coloring composition is also mentioned as a preferable thing as a (C-2) polymeric compound in the photosensitive deepening composition for black-matrix formation, What is shown below is especially preferable.

As a polymeric compound in the photosensitive deepening composition, it is preferable that it is a monomer or oligomer which has two or more ethylenically unsaturated double bonds, and add-polymerizes by light irradiation. Such monomers and oligomers include compounds having at least one addition polymerizable ethylenically unsaturated group in a molecule and having a boiling point of 100 ° C. or higher at atmospheric pressure. Examples thereof include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimethylol propane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated.

Acidic polyfunctional photocurable compounds are also preferred compounds. As an acidic polyfunctional photocurable compound, (1) the monomer or oligomer which has three or more photocurable functional groups with a hydroxyl group introduce | transduced the carboxyl group by denaturation with a dibasic acid anhydride, (2) three or more photocurable functional groups with a hydroxyl group Introducing a carboxyl group by adding a glycidyl group or a compound having an isocyanate group and a COOH group to a monomer or oligomer having the same, or (3) by modifying an aromatic compound having three or more photocurable functional groups with concentrated sulfuric acid or fuming sulfuric acid The thing which introduced the sulfonic acid group, etc. can be used. Moreover, you may use the oligomer which contains the monomer which is an acidic polyfunctional photocurable compound itself as a repeating unit, as an acidic polyfunctional photocurable compound.

As an example of an acidic polyfunctional photocurable compound, it is preferable to represent with the following general formula (i) and general formula (ii). On the other hand, in general formula (i) and general formula (ii), when T or G is an oxyalkylene group, the terminal at the side of a carbon atom couple | bonds with R, X, and W. As shown to FIG.

In the general formula (i), R is a (meth) acryloyl group represents an acryloyloxy, X represents a -COOH group or a -OPO ₃ H _2. T represents an oxyalkylene group, wherein the alkylene group has 1 to 4 carbon atoms. n is 0-20.

In general formula (ii), W represents R or X in general formula (i), and three or more W out of six W is R. G is the same as T in General formula (i). Z represents -O- or -OC = ONH (CH ₂ ) qNHCOO-. p is 0-20 and q is 1-8. Two or more R, X, T, G in one molecule may be same or different, respectively.

As a commercial item of the acidic polyfunctional photocurable compound represented by general formula (i) and general formula (ii), TOAGOSEI Co., Ltd., for example. TO-756 which is a carboxyl group-containing trifunctional acrylate of a product, TO-1382 which is a carboxyl group-containing 5-functional acrylate, etc. are mentioned.

Urethane acrylates described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193; Polyester acrylates described in Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191 and Japanese Patent Laid-Open No. 52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the carboxyl group-containing 5-functional acrylate desirable. In addition, "polymerizable compound B" described in Unexamined-Japanese-Patent No. 11-133600 is also mentioned as a preferable thing.

As content of the (C-2) polymeric compound in the photosensitive deepening composition used for forming a black matrix, it is preferable that it is 5-50 mass% in all solid content of the photosensitive deepening composition layer, and it is more preferable that it is 7-40 mass%. It is preferable and it is more preferable that it is 10-35 mass%.

The (B) binder polymer, (D) polymerization initiator, (E) solvent, other additives, etc. which are used for the photosensitive deepening composition are the same as those in the photosensitive coloring composition for coloring pattern formation mentioned above, and their preferable content is also the same.

<Color filter>

The color filter of this invention is a color filter manufactured by the manufacturing method of the color filter of the said invention. As for the color filter manufactured by the manufacturing method of the color filter of the said invention, thinning of a thin line is suppressed, for example, and the coloring pixel (coloring pattern) and development are favorable, and the color omission of a coloring pixel is suppressed. In addition, the color filter manufactured by the method for producing a color filter of the present invention has a voltage holding ratio of, for example, 95% or more because of improving the voltage holding ratio.

<LCD display device>

The liquid crystal display device of the present invention is a liquid crystal display device having the color filter of the present invention. Therefore, a high quality image can be displayed.

The definition of the display device and the description of each display device are described in, for example, "Electronic display device (Akio Sasaki by Kogyo Chosakai Publishing, Inc. 1990)", "Display device (by Ikiki Sumiaki, Sangyo-tosho Publishing Co. 1989). Issuance). In addition, the liquid crystal display device is described in "Next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing, Inc. 1994 issuance)", for example. There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to liquid crystal display devices of various methods described in the "next-generation liquid crystal display technology".

The present invention is particularly effective for a color TFT type liquid crystal display device. The liquid crystal display device of the color TFT system is described, for example, in "Color TFT liquid crystal display (KYORITSU SHUPPAN Co., Ltd. 1996 issuance)". In addition, the present invention can be applied to liquid crystal display devices having enlarged viewing angles such as lateral electric field driving methods such as IPS and pixel division methods such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. have. These methods are described, for example, on page 43 of EL, PDP, LCD display technology and the latest trends in the market (Toray Research Center Inc., Research and Research, 2001).

In addition to the color filter, the liquid crystal display is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The board | substrate with a light shielding film of this invention is applicable to the liquid crystal display device comprised from these well-known members.

For these members, for example, the '94 market liquid crystal display peripheral materials and chemicals (Kentaro CMC Co., Ltd. 1994 issuance), '' the 2003 liquid crystal market and the future prospects (the lower volume) (Ryomoto Omote Fuji) Chimera Research Institute, Inc., 2003).

Backlights are described in SID Meeting Digest 1380 (2005) (A. Konno et. Al), pages 18-24 (Toya Suhiro) of the December 2005 issue of Monthly Display, pages 25-30 (Yagi Takaaki), and the like.

The color filter of the present invention realizes high contrast when it is combined with a three-wavelength tube of a conventionally known cold cathode tube. However, the red, green, and blue LED light source (RGB-LED) is used as a backlight for high luminance and high color reproducibility. A good liquid crystal display device can be provided.

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, reagents, ratios, instruments, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below. In addition, unless otherwise indicated in a following example, "%" and "part" show the "mass%" and the "mass part", and molecular weight shows a weight average molecular weight.

(Example 1)

<1. Preparation of Photosensitive Deep Color Composition>

Preparation of Carbon Black Dispersion (K-1)

The carbon black dispersion (K-1) was prepared by the following prescription.

Carbon black (color black FW2 from Evanonic Degussa Japan Co., Ltd.)

Dispersant (KUSUMOTO CHEMICAL, Ltd.Disparon DA7500 Acid Value 26 Amine Value 40)

Part 3.3

Benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) copolymer

(Molecular weight 30,000, 50 mass% solution of propylene glycol monomethyl ether acetate)

Propylene glycol monomethyl ether acetate

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The obtained mixed solution was undispersed by the bead disperser (brand name: DISPERMAT, VMA-GETZMANN GMBH Process engineering product) using 0.3 mm zirconia beads, and carbon black dispersion liquid (K-1) was obtained for 8 hours.

Using the obtained carbon black dispersion (K-1), the photosensitive deep color composition coating liquid CK-1 was prepared by the following prescription.

Dispersion (K-1) ... 31.0 g

Resin solution ············· 3.0 g

(Benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (molecular weight 10000, 50 mass% solution of propylene glycol monomethyl ether acetate)

UV curable resin ... 2.0 g ··········

(Product name CYCLOMER PACA-250 DAICEL CHEMICAL INDUSTRIES, LTD.Product [Acrylic copolymer with alicyclic, COOH and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)))

Polymerizable Compounds 2.2 g

(Brand name TO-1382 TOAGOSEI Co., Ltd. (The monomer which has a 5-functional acryloyl group which substituted a part of terminal OH group of dipentaerythritol pentaacrylate with COOH group as a main component.)

Initiator · 0.8g ·················

(Product name `` OXE-02 '' Ciba Specialty Chemicals product)

Polymerization inhibitor (methoxy phenol) 0.0002 g

Surfactant: 0.001 g

(Product name `` MEGAFAC ER30 '' DIC Corporation product)

Solvent Propylene Glycol Monomethyl Ether Acetate17.6g

Methyl ethyl ketone ... 34.7 g

Cyclohexanone ... 8.7 g

<2. Formation of Black Matrix by Application>

Photosensitive deep color composition layer forming process

Using the slit coater (Model No. HC6000, product of Hirata Corporation) on a glass substrate (Corning Incorporated Millennium 0.7mm thick), the obtained photosensitive deepening composition CK-1 was used to provide a thickness and a discharge amount between the slit and the glass substrate so that the thickness after the postbaking was 2.0 µm. Was adjusted and applied at a coating speed of 120 mm / sec. And about the formed coating film, it heated at 90 degreeC for 120 second (drying process: prebaking process) using the hotplate, and formed the photosensitive deep color composition layer.

Exposure process

Next, the formed photosensitive deep color composition layer was exposed at 100 mJ / cm 2 using a mirror projection method exposure machine (model number MPA-8000, manufactured by Canon Inc.).

Development Process

Subsequently, the shower pressure was lowered with 1.0% developer (1 part by mass of CDK-1, 99 parts by mass of pure water, 25 ° C.) of potassium hydroxide-based developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.). It was set to 0.20 MPa, developed for 60 seconds, washed with pure water to obtain a black matrix after development.

Baking Process

Then, a postbaking treatment was performed for 40 minutes in a clean oven at 220 ° C., and the lattice in which the opening of the colored pixel formation region was 90 μm × 200 μm, the thickness of the black matrix was 2.0 μm, and the line width of the black matrix was about 25 μm. A phase black matrix substrate was formed.

It was 4.0 when the optical density (OD) of the completed black matrix was measured using X-Rite 361T (V) (made by SAKATA INX ENG. CO., LTD.).

<3. Preparation of Photosensitive Coloring Composition>

-3-1. Preparation of photosensitive coloring composition coating liquid CR-1 for red (R)-

The dispersion (R-1) for red (R) was prepared with the following prescription.

Pigment Red 254 (average particle size 43 nm in SEM observation) 11 parts

Pigment Red 177 (average particle diameter 58 nm in SEM observation)

Dispersion resin A-3 shown below ... 5 parts

Dispersant (trade name: Disperbyk-161, manufactured by BYK-Chemie GmbH)

(30% solution of propylene glycol monomethyl ether acetate)

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

(= 75/25 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) .. 9 parts

Solvent B: Propylene glycol monomethyl ether acetate

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The obtained mixed solution was undispersed for 4 hours using a bead disperser (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH Process engineering) using 0.3 mm zirconia beads to obtain a dispersion (R-1) for red (R).

The photosensitive coloring composition coating liquid CR-1 for red (R) was prepared by the following prescription using the obtained dispersion (R-1) for red (R).

Dispersion liquid (R-1) for red (R) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine ··················· 1g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -butanone-1

Polymerization Initiator: Diethyl Thioxanthone 0.5 g

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based Surfactant0.01 g

(Brand name: product of MEGAFAC R30 DIC Corporation)

Nonionic Surfactant0.2g

(Brand name: product of TETRONIC R150 ADEKA)

Solvent: Propylene glycol monomethyl ether acetate 27.7 g

 Methyl ethyl ketone ...... 81.8 g

 Cyclohexanone ・ ・ ・ ・ ・ 20.5 g

The said component was mixed and stirred, and the photosensitive coloring composition coating liquid CR-1 for red (R) was obtained.

-3-2. Preparation of photosensitive coloring composition coating liquid CG-1 for green (G)-

The dispersion (G-1) for green (G) was prepared by the following prescription.

Pigment Green 36 (mean particle diameter 47 nm in SEM observation) 11 parts

Pigment Yellow 150 (average particle diameter 39 nm in SEM observation)

Dispersion resin A-3 shown below ... 5 parts

Dispersant (trade name: Disperbyk-161, 30% solution from BYK-Chemie GmbH)

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer (= 85/15 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%))

Solvent: Propylene glycol monomethyl ether acetate

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The obtained mixed solution was undispersed for 8 hours using a beads disperser (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH Process engineering) using 0.3 mm zirconia beads to obtain a dispersion (G-1) for green (G).

The photosensitive coloring composition coating liquid CG-1 for green (G) was prepared by the following prescription using the obtained dispersion (G-1) for green (G).

Dispersion solution for green (G-1) ················ 100

Epoxy resin ... 2 g

(Product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerizable compound: pentaerythritol tetra (ethoxy acrylate) 2 g

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolatriazine-2 g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactant ... 0.5g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 37.3 g

 Methyl ethyl ketone ... 90.2 g

 Cyclohexanone ・ ・ ・ ・ ················ 22.6 g

The said composition was mixed and stirred, and the photosensitive coloring composition coating liquid CG-1 for green (G) was obtained.

-3-3. Preparation- of photosensitive coloring composition coating liquid CB-1 for blue (B)

The dispersion (B-1) for blue (B) was prepared by the following prescription.

Pigment Blue 15: 6 (average particle diameter 55 nm in SEM observation)

Pigment Violet 23 (average particle diameter 61 nm in SEM observation)

Dispersion resin A-3 shown below ... 5 parts

Dispersant (trade name: Disperbyk-161, 30% solution from BYK-Chemie GmbH)

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 4 parts

Solvent: Propylene glycol monomethyl ether acetate73 parts

Each said component was stirred for 1 hour using the homogenizer on 3000 rpm conditions. The resulting mixed solution was microdispersed for 4 hours using a bead disperser (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH Process engineering) using 0.3 mm zirconia beads to obtain a dispersion (B-1) for blue (B).

The photosensitive coloring composition coating liquid CB-1 for blue (B) was prepared by the following prescription using the obtained dispersion (B-1) for blue (B).

Dispersion liquid for blue (B) (B-1) ... 100 g

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

(= 80/20 [molar ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 7 g

Epoxy resin ... 2 g

(Product name CELLOXIDE 2080 DAICEL CHEMICAL INDUSTRIES, LTD.)

UV-curable resin 4 g

(Product name CYCLOMER P ACA-250 DAICEL CHEMICAL INDUSTRIES, LTD.)

(Acrylic copolymer with alicyclic ring, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)

Polymerizable compound: dipentaerythritol penta hexaacrylate 12 g

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone 3 g ············· 3 g

· Polymerization inhibitor: p-methoxy phenol ··············· 0.001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactants 1.0 g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 44.8 g

 Methyl ethyl ketone ..... 100 g

 Cyclohexanone ・ ・ ・ ・ ・ 25.1 g

The said component was mixed and stirred, and the photosensitive coloring composition coating liquid CB-1 for blue (B) was obtained.

<4. Synthesis of Dispersion Resin A-3>

(1.Synthesis of Chain Transfer Agent A3)

Dipentaerythritol hexakis (3-mercapto propionate) [DPMP; SAKAI CHEMICAL INDUSTRY Co., Ltd.] (the following compound (33)) and 4.55 parts of the following compound (m-6) which have an adsorption site and also has a carbon-carbon double bond are dissolved in 28.90 parts of propylene glycol monomethyl ether. It heated at 70 degreeC under nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) [V-65, Wako Pure Chemical Industries, Ltd. Product] 0.04 parts were added and heated for 3 hours. Further, 0.04 parts of V-65 was added and reacted at 70 ° C for 3 hours under a nitrogen stream. The 30% solution of the mercaptan compound (chain transfer agent A3) shown below was obtained by cooling to room temperature.

(2.Synthesis of Dispersion Resin A-3)

The mixed solution of 4.99 parts of 30% solution of the chain transfer agent A3 obtained above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether was heated at 90 degreeC under nitrogen stream. 2,2'- azobisisobutyric acid dimethyl [V-601, Wako Pure Chemical Industries, Ltd., stirring this mixed solution. Product] A mixed solution of 0.139 parts, 5.36 parts of propylene glycol monomethyl ether and 9.40 parts of propylene glycol monomethyl ether acetate was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was reacted at 90 ° C for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2'-azobisisobutyric acid and 4.00 parts of propylene glycol monomethyl ether acetate was added and reacted for another 2 hours. 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added to a reaction liquid, and it cooled to room temperature, and the solution of specific dispersion resin A-3 (weight average molecular weight 24000 of polystyrene conversion) (30 mass% of specific dispersion resin) And 21 mass% of propylene glycol monomethyl ether and 49 mass% of propylene glycol monomethyl ether acetate) were obtained.

The acid value of this specific dispersion resin A-3 was 48 mg / g. The structure of dispersion resin A-3 is shown below.

<Production of color filter>

Photosensitive coloring composition layer forming process

The obtained photosensitive coloring composition coating liquid CR-1 for red (R) was apply | coated to the black-matrix formation surface side of the said black-matrix board | substrate. Specifically, as in the case of forming the photosensitive deep color composition layer, the interval between the slit and the black matrix substrate and the discharge amount were adjusted so that the layer thickness of the photosensitive colored composition layer after post-baking was about 2.1 μm, and the coating speed was applied at 120 mm / sec and heated ( Prebaking treatment).

Colored layer exposure process

Then, it exposed at 90 mJ / cm <2> using the mirror projection system exposure machine (model number MPA-8000, Canon Inc. product).

Colored layer developing process, colored layer baking process

Subsequently, the shower pressure was reduced with 1.0% developer (1 part by mass of CDK-1 and 99 parts by mass of pure water, 25 ° C) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.). It set for 0.2 MPa, developed for 45 second, and wash | cleaned with pure water.

Thereafter, the substrate was post-baked in a clean oven at 220 ° C. for 30 minutes to form a heat-treated red pixel.

Next, in the said photosensitive coloring composition layer forming process, a colored layer prebaking process, a colored layer exposure process, a colored layer developing process, and a colored layer baking process, the photosensitive coloring composition coating liquid CR-1 for red (R) is green. The green pixel was similarly formed except having replaced with the photosensitive coloring composition coating liquid CG-1 for (G). Furthermore, except having changed the photosensitive coloring composition coating liquid CR-1 for red (R) into the photosensitive coloring composition coating liquid CB-1 for blue (B), blue pixels were similarly formed and the color filter was obtained.

[evaluation]

<Measurement of Residual Solvent>

The residual solvent amount of the colored liquid composition layer (photosensitive deepening composition layer, photosensitive coloring composition layer) for forming the black matrix of the obtained color filter and each color pixel was measured as follows.

The formation of each of the colored liquid composition layers was carried out in a similar manner except that a 75 μm base was deposited on the glass substrate, and the composition layer immediately after heating on a hot plate under the same prebaking conditions (after 5 seconds). The formed 75㎛ PET is precisely punctured 10cm × 10cm and finely cut. The cuts were sealed in a 22 cc vial container, and sealed in a gas chromatograph (trade name; Capillary Gas Chromatograph (model number; GC-2010) manufactured by Shimadzu Corporation), column (trade name; Capillary Column (volatile compound analysis column) (model number; DB). -VRX) manufactured by J & W SCIENTIFIC Inc., and MMPG-Ac, MEK, cyclohexanone, and 3-ethoxyethylpropionate were calculated from the calibration curve previously measured.

<Measurement of line width>

The line width of the black matrix formed on the obtained color filter was measured using the line width measuring system MIM-L (manufactured by MIKASA Co., Ltd.). Moreover, the line width of the mask used for exposure is also shown with a measurement result.

<Measurement of voltage holding ratio>

The color filter produced above is scraped off and weighed 0.015 g. The chopped sample is added to 0.52 g of liquid crystal (nematic liquid crystal; trade name MLC-6608, manufactured by Merck & Co., Inc.) and boiled at 120 ° C for 1 hour. The supernatant of the boiled liquid crystal was filled into a glass cell of 2 cm x 2.5 cm by suction, sealed with a sealant (trade name UV-REJIN, model number LCB-601, EHC), and UV cured to produce a liquid crystal cell. A DC voltage was applied between the liquid crystal cells, and the voltage was measured after the elapsed time was maintained at 50 ° C for 16.7 milliseconds, and the comparison of the voltage with the blank without inserting the sample from which the color filter was removed was referred to as the voltage retention. . (%; = Voltage retention of the liquid crystal injecting the photosensitive resin composition / voltage retention of the liquid crystal not injecting the photosensitive resin composition)

(Example 2)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive deepening composition coating liquid CK-1 into 100 degreeC.

(Example 3)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive coloring composition coating liquid CR-1 for red (R) into 100 degreeC.

(Example 4)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive coloring composition coating liquid CG-1 for green (G) into 100 degreeC.

(Example 5)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive coloring composition coating liquid CB-1 for blue (B) into 100 degreeC.

(Example 6)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive deepening composition coating liquid CK-1 at 100 degreeC for 150 second.

(Example 7)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive coloring composition coating liquid CR-1 for red (R) into 100 second at 150 degreeC.

(Example 8)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive coloring composition coating liquid CG-1 for green (G) into 150 second at 100 degreeC.

(Example 9)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the prebaking temperature of the photosensitive coloring composition coating liquid CB-1 for blue (B) into 100 second at 150 degreeC.

(Example 10)

In Example 1, the color filter was produced and evaluated like Example 1 except having made the coating method spin-coating (HI-DX (made by MIKASA Co., Ltd.).

(Example 11)

In Example 1, photosensitive color composition composition liquid CK-1, photosensitive coloring composition coating liquid CR-1 for red (R), photosensitive coloring composition coating liquid CG-1 for green (G), photosensitive coloring for blue (B) The color filter was produced and evaluated like Example 1 except having changed the prescription of the composition coating liquid CB-1 below.

<Photosensitive darkening composition coating liquid CK-2>

Dispersion (K-1) ... 31.0 g

Resin solution: 3.0 g ··············

(Benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (molecular weight 10000, 50 mass% solution of propylene glycol monomethyl ether acetate)

UV curable resin 2.0 g

(Product name CYCLOMER P ACA-250 DICEL CHEMICAL INDUSTRIES, LTD.Product [Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass))

Polymerizable compound ... 2.2 g

(Brand name TO-1382 TOAGOSEI Co., LTD.Product (The monomer which has a 5-functional acryloyl group which substituted a part of terminal OH group of dipentaerythritol pentaacrylate with COOH group as a main component.)

Initiator ... 0.8g

(Product name `` OXE-02 '' Ciba Specialty Chemicals product)

Polymerization inhibitor (methoxy phenol) 0.0002 g

Surfactant: 0.001 g

(Product name `` MEGAFAC R30 '' DIC Corporation product)

Solvent: Propylene glycol monomethyl ether acetate 46.0 g

 3-ethoxyethylpropionate (EEP) 15.0 g

<Photosensitive coloring composition coating liquid CR-2 for red (R)>

Dispersion (R-1) for red (R) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine ······················· 1g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorinated Surfactants0.01 g

(Brand name: product of MEGAFAC R30 DIC Corporation)

Nonionic Surfactant ... 0.2g

(Brand name: product of TETRONIC R150 ADEKA company)

Solvent: Propylene glycol monomethyl ether acetate 110.0 g

 3-ethoxyethylpropionate (EEP) ... 20.0 g

<Photosensitive coloring composition coating liquid CG-2 for green (G)>

Dispersion (G-1) for green (G) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerizable compound: pentaerythritol tetra (ethoxy acrylate) 2 g

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolatriazine-2 g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactant ... 0.5g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 120.1 g

 3-ethoxyethylpropionate (EEP) 30.0 g

<Photosensitive coloring composition coating liquid CB-2 for blue (B)>

Dispersion liquid for blue (B) (B-1) ... 100 g

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

(= 80/20 [molar ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 7 g

Epoxy resin ... 2 g

(Product name CELLOXIDE 2080 DAICEL CHEMICAL INDUSTRIES, LTD.)

UV-curable resins ... 4 g

(Product name CYCLOMER P ACA-250 DAICEL CHEMICAL INDUSTRIES, LTD.)

(Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)

Polymerizable compound: dipentaerythritol penta hexaacrylate 12 g

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone 3 g ············· 3 g

Polymerization inhibitor: p-methoxy phenol: 0.001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactants 1.0 g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 139.9 g

3-ethoxyethylpropionate (EEP) 30.0 g

(Comparative Example 1)

In Example 1, the color filter was produced like Example 1 except having set the prebaking temperature of the photosensitive deepening composition coating liquid CK-1 to 70 degreeC.

(Example 12)

In Example 1, the color filter was produced like Example 1 except having made the prebaking time of the photosensitive rich composition coating liquid CK-1 into 60 second.

(Comparative Example 2)

In Example 1, photosensitive color composition composition liquid CK-1, photosensitive coloring composition coating liquid CR-1 for red (R), photosensitive coloring composition coating liquid CG-1 for green (G), photosensitive coloring for blue (B) A color filter was produced in the same manner as in Example 1 except that the prebaking time of the composition coating liquid CB-1 was 90 ° C and 60 seconds.

(Example 13)

In Example 1, the photosensitive color composition coating liquid CK-1, the photosensitive coloring composition coating liquid CR-1 for red (R), the photosensitive coloring composition coating liquid CG-1 for green (G), and the photosensitive property for blue (B) The color filter was produced and evaluated like Example 1 except having changed the prescription of the coloring composition coating liquid CB-1 below.

<Photosensitive deepening composition coating liquid CK-3> A solvent amount of boiling point 100 degreeC or more is 24.0%

Dispersion (K-1) ... 31.0 g

Resin solution: 3.0 g ··············

(Benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (molecular weight 10000, 50 mass% solution of propylene glycol monomethyl ether acetate)

UV curable resin ... 2.0 g

(Product name CYCLOMER P ACA-250 DICEL CHEMICAL INDUSTRIES, LTD.Product [Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass))

Polymerizable compound ... 2.2 g

(Product name TO-1382 TOAGOSEI Co., LTD.Product (The main component is a monomer having a 5-functional acryloyl group in which a part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group.)

Initiator ... 0.8g

(Product name `` OXE-02 '' Ciba Specialty Chemicals product)

Polymerization inhibitor (methoxy phenol) 0.0002 g

Surfactant: 0.001 g

(Product name `` MEGAFAC R30 '' DIC Corporation product)

Solvent: Methyl ethyl ketone ... 61.0 g

<Photosensitive coloring composition coating liquid CR-3 for red (R)> The solvent amount of boiling point 100 degreeC or more is 29.0%

Dispersion liquid (R-1) for red (R) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine ····················· 1g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based Surfactant0.01 g

(Brand name: product of MEGAFAC R30 DIC Corporation)

Nonionic Surfactant ... 0.2g

(Brand name: product made in TETRONIC R150 ADEKA company)

Solvent: Methyl ethyl ketone ... 156.6 g

<Photosensitive coloring composition coating liquid CG-3 for green (G)> The solvent amount of boiling point 100 degreeC or more is 29.0%

Dispersion solution (G-1) for green (G) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerizable compound: pentaerythritol tetra (ethoxy acrylate) 2 g

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolatriazine-2 g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactant ... 0.5g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Methyl ethyl ketone ... 156.4 g

<Photosensitive coloring composition coating liquid CB-3 for blue (B)> The solvent amount of boiling point 100 degreeC or more is 29.8%

Dispersion liquid for blue (B) (B-1) ... 100 g

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

(= 80/20 [molar ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 7 g

Epoxy resin ... 2 g

(Product name CELLOXIDE 2080 DAICEL CHEMICAL INDUSTRIES, LTD.)

UV-curable resins 4 g ··········

(Product name CYCLOMER P ACA-250 DAICEL CHEMICAL INDUSTRIES, LTD.)

(Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass))

Polymerizable compound: dipentaerythritol penta hexaacrylate 12 g

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone 3 g ············· 3 g

Polymerization inhibitor: p-methoxy phenol: 0.001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactants 1.0 g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Methyl ethyl ketone ... 169.9 g

Here, in Example 13, although the residual solvent amount, the voltage holding ratio, and the line width were satisfactory, nozzle clogging due to drying of the colored liquid composition at the tip of the slit nozzle of the slit coater was likely to occur.

(Comparative Example 3)

In Example 1, photosensitive color composition composition liquid CK-1, photosensitive coloring composition coating liquid CR-1 for red (R), photosensitive coloring composition coating liquid CG-1 for green (G), photosensitive coloring for blue (B) The color filter was produced and evaluated like Example 1 except having changed the prescription of the composition coating liquid CB-1 below.

<Photosensitive deepening composition coating liquid CK-4> The solvent amount of boiling point 100 degreeC or more is 77.6%

Dispersion (K-1) ... 31.0 g

Resin solution: 3.0 g ··············

(Benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (molecular weight 10000, 50 mass% solution of propylene glycol monomethyl ether acetate)

UV curable resin ... 2.0 g

(Product name CYCLOMER P ACA-250 DICEL CHEMICAL INDUSTRIES, LTD.

Polymerizable compound ... 2.2 g

(Brand name TO-1382 TOAGOSEI Co., LTD. (The monomer which has a 5-functional acryloyl group which substituted a part of terminal OH group of dipentaerythritol penta acrylate with a COOH group as a main component.)

Initiator · 0.8g ·················

(Product name `` OXE-02 '' Ciba Specialty Chemicals product)

Polymerization inhibitor (methoxy phenol) 0.0002 g

Surfactant: 0.001 g

(Product name `` MEGAFAC R30 '' DIC Corporation product)

Solvent: Propylene glycol monomethyl ether acetate 53.35 g

        Methyl ethyl ketone ... 7.75 g

<Photosensitive coloring composition coating liquid CR-4 for red (R)> The solvent amount of boiling point 100 degreeC or more is 73.5%

Dispersion liquid (R-1) for red (R) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine ····················· 1g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based Surfactant0.01 g

(Brand name: product of MEGAFAC R30 DIC Corporation)

Nonionic Surfactant ... 0.2g

(Brand name: product of TETRONIC R150 ADEKA company)

Solvent: Propylene glycol monomethyl ether acetate 100.15 g

 Methyl ethyl ketone ... 29.65 g

<Photosensitive coloring composition coating liquid CG-4 for green (G)> The solvent amount of boiling point 100 degreeC or more is 71.00%

Dispersion solution (G-1) for green (G) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerizable compound: pentaerythritol tetra (ethoxy acrylate) 2 g

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolatriazine-2 g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactant ... 0.5g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 109.95 g

 Methyl ethyl ketone ... 40.15 g

<Photosensitive coloring composition coating liquid CB-4 for blue (B)> The solvent amount of boiling point 100 degreeC or more is 72.00%

Dispersion liquid for blue (B) (B-1) ... 100 g

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

(= 80/20 [molar ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 7 g

Epoxy resin ... 2 g

(Product name CELLOXIDE 2080 DAICEL CHEMICAL INDUSTRIES, LTD.)

UV-curable resins 4 g ···········

(Product name CYCLOMER P ACA-250 DAICEL CHEMICAL INDUSTRIES, LTD.)

(Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass))

Polymerizable compound: dipentaerythritol penta hexaacrylate 12 g

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone 3 g ············· 3 g

Polymerization inhibitor: p-methoxy phenol: 0.001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactants 1.0 g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 129.12 g

 Methyl ethyl ketone ... 40.78 g

(Comparative Example 4)

In Example 1, photosensitive color composition composition liquid CK-1, photosensitive coloring composition coating liquid CR-1 for red (R), photosensitive coloring composition coating liquid CG-1 for green (G), photosensitive coloring for blue (B) The color filter was produced and evaluated like Example 1 except having changed the prescription of the composition coating liquid CB-1 below.

<Photosensitive deepening composition coating liquid CK-5>

Dispersion (K-1) ... 31.0 g

Resin solution: 3.0 g ··············

(Benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (molecular weight 10000, 50 mass% solution of propylene glycol monomethyl ether acetate)

UV curable resin ... 2.0 g

(Product name CYCLOMER P ACA-250 DICEL CHEMICAL INDUSTRIES, LTD.Product [Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass))

Polymerizable compound ... 2.2 g

(Product name TO-1382 TOAGOSEI Co., LTD.)

(The main component is a monomer having a 5-functional acryloyl group in which a part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group)

Initiator ... 0.8g

(Product name `` OXE-02 '' Ciba Specialty Chemicals product)

Polymerization inhibitor (methoxy phenol) 0.0002 g

Surfactant: 0.001 g

(Product name `` MEGAFAC R30 '' DIC Corporation product)

Solvent: Propylene glycol monomethyl ether acetate 46.0 g

 Propylene glycol monomethyl ether (MFG) 15.0 g

<Photosensitive coloring composition coating liquid CR-5 for red (R)>

Dispersion liquid (R-1) for red (R) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine ····················· 1g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based Surfactant0.01 g

(Brand name: product of MEGAFAC R30 DIC Corporation)

Nonionic Surfactant ... 0.2g

(Brand name: product of TETRONIC R150 ADEKA company)

Solvent: Propylene glycol monomethyl ether acetate 110.0 g

 Propylene Glycol Monomethyl Ether (MFG) ... 20.0 g

<Photosensitive coloring composition coating liquid CG-5 for green (G)>

Dispersion solution (G-1) for green (G) ... 100 g

Epoxy resin ... 2 g

(Product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.)

Polymerizable compound: dipentaerythritol penta hexaacrylate 8 g

Polymerizable compound: pentaerythritol tetra (ethoxy acrylate) 2 g

Polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolatriazine-2 g

Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

Polymerization initiator: 0.5 g of diethyl thioxanthone

Polymerization inhibitor: p-methoxy phenol ... 1,001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactant ... 0.5g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 120.1 g

 Propylene glycol monomethyl ether (MFG) 30.0 g

<Photosensitive coloring composition coating liquid CB-5 for blue (B)>

Dispersion liquid for blue (B) (B-1) ... 100 g

Alkali-soluble resin: Benzyl methacrylate / methacrylic acid copolymer

(= 80/20 [molar ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) ... 7 g

Epoxy resin ... 2 g

(Product name CELLOXIDE 2080 DAICEL CHEMICAL INDUSTRIES, LTD.)

UV-curable resins 4 g ···········

(Product name CYCLOMER P ACA-250 DAICEL CHEMICAL INDUSTRIES, LTD.)

(Acrylic copolymer with alicyclic, COOH group and acryloyl group in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)

Polymerizable compound: dipentaerythritol penta hexaacrylate 12 g

Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyl oxime) ethanone 3 g ············· 3 g

Polymerization inhibitor: p-methoxy phenol: 0.001 g

Fluorine-based surfactants: 0.02 g

(A brand name: a product of MEGAFAC R08 DIC Corporation)

Nonionic Surfactants 1.0 g

(Brand name: product of EMULGEN A-60 KAO Corporation)

Solvent: Propylene glycol monomethyl ether acetate 139.9 g

 Propylene glycol monomethyl ether (MFG) 30.0 g

The above result is shown to Tables 1-3.

In addition, the solvent used by the Example and the comparative example is as follows.

MEK: Methyl ethyl ketone (boiling point: 80 ° C)

PGMEA: Propylene glycol monomethyl ether acetate (boiling point: 146 ° C)

EEP: 3-ethoxyethyl propionate (boiling point: 170 ° C)

Cyclohexanone (boiling point: 156 ° C)

MFG: Propylene glycol monomethyl ether (boiling point: 120 ° C)

From the above results, in the present embodiment in which the amount of residual solvent in the colored liquid composition layer immediately after prebaking was reduced, the developability was improved compared with the comparative example, and the voltage retention of the color filter obtained was improved to obtain a high quality image. I can see that there is.

Claims (13)

A method of manufacturing a color filter having two or more patterned colored pixels having different colors on a substrate and a black matrix around them: In order to form at least one colored pixel or black matrix, the residual solvent amount of the colored liquid composition layer immediately after forming and prebaking the colored liquid composition on the substrate is 10 µl / m 2 or less, and the colored pixels and the black matrix of each color The sum total of the amount of residual solvent of the said colored liquid composition layer to form is 40 microliters / m <2> or less, The manufacturing method of the color filter characterized by the above-mentioned. The method of claim 1, The method for forming the colored liquid composition is any one of a spinner method and a slit coater method. The method of claim 1, The said prebaking temperature is 60 degreeC or more and 140 degrees C or less, The prebaking time is 30 second or more and 300 second or less, The manufacturing method of the color filter characterized by the above-mentioned. It is obtained by the manufacturing method of Claim 1, The color filter characterized by the above-mentioned. As a color filter obtained by the manufacturing method according to claim 1: The solvent of the said colored liquid composition contains 30-70 weight% of solvents with a boiling point of 100 degreeC or more, The color filter characterized by the above-mentioned. As a color filter obtained by the manufacturing method according to claim 1: The solvent of the said colored liquid composition is at least 1 sort (s) chosen from propylene glycol monomethyl ether acetate, cyclohexanone, methyl ethyl ketone, and 3-ethoxy ethyl propionate. As a color filter obtained by the manufacturing method according to claim 1: The colored liquid composition comprises a polymer having a carboxylic acid in the side chain. The method of claim 7, wherein The colored liquid composition further comprises an epoxy resin. As a color filter obtained by the manufacturing method according to claim 1: The said colored liquid composition contains the coloring agent of 10 nm-100 nm of average particle size, The color filter characterized by the above-mentioned. As a color filter obtained by the manufacturing method according to claim 1: And the colored liquid composition contains an addition polymerizable compound having at least one ethylenically unsaturated double bond. As a color filter obtained by the manufacturing method according to claim 1: And said colored liquid composition contains at least one photopolymerization initiator. As a color filter obtained by the manufacturing method according to claim 1: Wherein said colored liquid composition contains at least one polymeric dispersant. The color filter obtained by the manufacturing method of Claim 1 is provided, The liquid crystal display device characterized by the above-mentioned.